skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Uranyl peroxide nanoclusters at high-pressure

Abstract

Here, U 60 ([UO 2(O 2)(OH)] 60 60– in water) is a uranyl peroxide nanocluster with a fullerene topology and O h symmetry. U 60 clusters can exist in crystalline solids or in liquids; however, little is known of their behavior at high pressures. We compressed the U 60-bearing material: Li 68K 12(OH) 20[UO 2(O 2)(OH)] 60(H 2O) 310 ( Fm3¯; a = 37.884 Å) in a diamond anvil cell to determine its response to increasing pressure. Three length scales and corresponding structural features contribute to the compression response: uranyl peroxide bonds (<0.5 nm), isolated single nanoclusters (2.5 nm), and the long-range periodicity of nanoclusters within the solid (>3.7 nm). Li 68K 12(OH) 20[UO 2(O 2)(OH)] 60(H 2O) 310 transformed to a tetragonal structure below 2 GPa and irreversibly amorphized between 9.6 and 13 GPa. The bulk modulus of the tetragonal U 60-bearing material was 25 ± 2 GPa. The pressure-induced amorphous phase contained intact U 60 clusters, which were preserved beyond the loss of long-range periodicity. The persistence of U 60 clusters at high pressure may have been enhanced by the interaction between U 60 nanoclusters and the alcohol pressure medium. Once formed, U 60 nanoclusters persist regardless ofmore » their associated long-range ordering—in crystals, amorphous solids, or solutions.« less

Authors:
ORCiD logo [1];  [2];  [3];  [4];  [2];  [5];  [2];  [1]
  1. Stanford Univ., Stanford, CA (United States)
  2. Univ. of Notre Dame, Notre Dame, IN (United States)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  4. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  5. Stanford Univ., Stanford, CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Materials Science of Actinides (MSA); SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1417666
Grant/Contract Number:  
AC02-76SF00515; NA0001974
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Materials Research
Additional Journal Information:
Journal Volume: 32; Journal Issue: 19; Journal ID: ISSN 0884-2914
Publisher:
Materials Research Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Turner, Katlyn M., Szymanowski, Jennifer E. S., Zhang, Fuxiang, Lin, Yu, McGrail, Brendan T., Mao, Wendy L., Burns, Peter C., and Ewing, Rodney C. Uranyl peroxide nanoclusters at high-pressure. United States: N. p., 2017. Web. doi:10.1557/jmr.2017.301.
Turner, Katlyn M., Szymanowski, Jennifer E. S., Zhang, Fuxiang, Lin, Yu, McGrail, Brendan T., Mao, Wendy L., Burns, Peter C., & Ewing, Rodney C. Uranyl peroxide nanoclusters at high-pressure. United States. doi:10.1557/jmr.2017.301.
Turner, Katlyn M., Szymanowski, Jennifer E. S., Zhang, Fuxiang, Lin, Yu, McGrail, Brendan T., Mao, Wendy L., Burns, Peter C., and Ewing, Rodney C. Mon . "Uranyl peroxide nanoclusters at high-pressure". United States. doi:10.1557/jmr.2017.301. https://www.osti.gov/servlets/purl/1417666.
@article{osti_1417666,
title = {Uranyl peroxide nanoclusters at high-pressure},
author = {Turner, Katlyn M. and Szymanowski, Jennifer E. S. and Zhang, Fuxiang and Lin, Yu and McGrail, Brendan T. and Mao, Wendy L. and Burns, Peter C. and Ewing, Rodney C.},
abstractNote = {Here, U60 ([UO2(O2)(OH)]60 60– in water) is a uranyl peroxide nanocluster with a fullerene topology and O h symmetry. U60 clusters can exist in crystalline solids or in liquids; however, little is known of their behavior at high pressures. We compressed the U60-bearing material: Li68K12(OH)20[UO2(O2)(OH)]60(H2O)310 (Fm3¯; a = 37.884 Å) in a diamond anvil cell to determine its response to increasing pressure. Three length scales and corresponding structural features contribute to the compression response: uranyl peroxide bonds (<0.5 nm), isolated single nanoclusters (2.5 nm), and the long-range periodicity of nanoclusters within the solid (>3.7 nm). Li68K12(OH)20[UO2(O2)(OH)]60(H2O)310 transformed to a tetragonal structure below 2 GPa and irreversibly amorphized between 9.6 and 13 GPa. The bulk modulus of the tetragonal U60-bearing material was 25 ± 2 GPa. The pressure-induced amorphous phase contained intact U60 clusters, which were preserved beyond the loss of long-range periodicity. The persistence of U60 clusters at high pressure may have been enhanced by the interaction between U60 nanoclusters and the alcohol pressure medium. Once formed, U60 nanoclusters persist regardless of their associated long-range ordering—in crystals, amorphous solids, or solutions.},
doi = {10.1557/jmr.2017.301},
journal = {Journal of Materials Research},
number = 19,
volume = 32,
place = {United States},
year = {2017},
month = {8}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 3 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Designing intermediate-range order in amorphous materials
journal, September 2002

  • Martin, James D.; Goettler, Stephen J.; Fossé, Nathalie
  • Nature, Vol. 419, Issue 6905
  • DOI: 10.1038/nature01022

Amorphous Diamond: A High-Pressure Superhard Carbon Allotrope
journal, October 2011


Uranyl−Peroxide Interactions Favor Nanocluster Self-Assembly
journal, November 2009

  • Sigmon, Ginger E.; Ling, Jie; Unruh, Daniel K.
  • Journal of the American Chemical Society, Vol. 131, Issue 46
  • DOI: 10.1021/ja907837u

Hybrid Uranium-Oxalate Fullerene Topology Cage Clusters
journal, August 2010

  • Ling, Jie; Wallace, Christine M.; Szymanowski, Jennifer E. S.
  • Angewandte Chemie International Edition, Vol. 49, Issue 40
  • DOI: 10.1002/anie.201003197

Effective hydrostatic limits of pressure media for high-pressure crystallographic studies
journal, January 2007

  • Angel, Ross J.; Bujak, Maciej; Zhao, Jing
  • Journal of Applied Crystallography, Vol. 40, Issue 1
  • DOI: 10.1107/S0021889806045523

Single-Wall Carbon Nanotubes under High Pressures to 62 GPa Studied Using Designer Diamond Anvils
journal, June 2001

  • Patterson, Jeremy R.; Vohra, Yogesh K.; Weir, Samuel T.
  • Journal of Nanoscience and Nanotechnology, Vol. 1, Issue 2
  • DOI: 10.1166/jnn.2001.026

Nuclear Fuel in a Reactor Accident
journal, March 2012

  • Burns, Peter C.; Ewing, Rodney C.; Navrotsky, Alexandra
  • Science, Vol. 335, Issue 6073
  • DOI: 10.1126/science.1211285

The structural response of gadolinium phosphate to pressure
journal, September 2016

  • Heffernan, Karina M.; Ross, Nancy L.; Spencer, Elinor C.
  • Journal of Solid State Chemistry, Vol. 241
  • DOI: 10.1016/j.jssc.2016.06.009

Medium-range ordering in non-crystalline solids
journal, February 1987


X-ray Raman scattering studies on C60 fullerenes and multi-walled carbon nanotubes under pressure
journal, April 2007

  • Kumar, Ravhi S.; Pravica, Michael G.; Cornelius, Andrew L.
  • Diamond and Related Materials, Vol. 16, Issue 4-7
  • DOI: 10.1016/j.diamond.2006.11.103

Studtite, [(UO 2 )(O 2 )(H 2 O) 2 ](H 2 O) 2 : The first structure of a peroxide mineral
journal, July 2003

  • Burns, Peter C.; Hughes, Karrie-Ann
  • American Mineralogist, Vol. 88, Issue 7
  • DOI: 10.2138/am-2003-0725

Finite Elastic Strain of Cubic Crystals
journal, June 1947


Pressure-Induced Bond Rearrangement and Reversible Phase Transformation in a Metal-Organic Framework
journal, April 2014

  • Spencer, Elinor C.; Kiran, Mangalampalli S. R. N.; Li, Wei
  • Angewandte Chemie International Edition, Vol. 53, Issue 22
  • DOI: 10.1002/anie.201310276

Processing used nuclear fuel with nanoscale control of uranium and ultrafiltration
journal, May 2016


Specific volume measurements of Cu, Mo, Pd, and Ag and calibration of the ruby R 1 fluorescence pressure gauge from 0.06 to 1 Mbar
journal, June 1978

  • Mao, H. K.; Bell, P. M.; Shaner, J. W.
  • Journal of Applied Physics, Vol. 49, Issue 6
  • DOI: 10.1063/1.325277

On the Origin of the Cation Templated Self-Assembly of Uranyl-Peroxide Nanoclusters
journal, December 2010

  • Miró, Pere; Pierrefixe, Simon; Gicquel, Mickaël
  • Journal of the American Chemical Society, Vol. 132, Issue 50
  • DOI: 10.1021/ja1053175

Gallium Arsenate Dihydrate under Pressure: Elastic Properties, Compression Mechanism, and Hydrogen Bonding
journal, July 2015


Nanoscale Atoms in Solid-State Chemistry
journal, June 2013


The high pressure behaviour of the 3D copper carbonate framework {[Cu(CO 3 ) 2 ](CH 6 N 3 ) 2 } n
journal, January 2012

  • Spencer, Elinor C.; Ross, Nancy L.; Angel, Ross J.
  • J. Mater. Chem., Vol. 22, Issue 5
  • DOI: 10.1039/C2JM15206A

The influence of pressure on the structure of a 2D uranium(VI) carboxyphosphonoate compound
journal, October 2014

  • Spencer, Elinor C.; Ross, Nancy L.; Surbella, Robert G.
  • Journal of Solid State Chemistry, Vol. 218
  • DOI: 10.1016/j.jssc.2014.05.026

Actinyl Peroxide Nanospheres
journal, March 2005

  • Burns, Peter C.; Kubatko, Karrie-Ann; Sigmon, Ginger
  • Angewandte Chemie International Edition, Vol. 44, Issue 14
  • DOI: 10.1002/anie.200462445

U6+ Minerals and Inorganic Compounds: Insights into an Expanded Structural Hierarchy of Crystal Structures
journal, December 2005


Diamond anvil cell, 50th birthday
journal, May 2009


Electronic structure and bonding in icosahedral C60
journal, April 1986


Pressure-Induced Conductivity and Yellow-to-Black Piezochromism in a Layered Cu–Cl Hybrid Perovskite
journal, January 2015

  • Jaffe, Adam; Lin, Yu; Mao, Wendy L.
  • Journal of the American Chemical Society, Vol. 137, Issue 4
  • DOI: 10.1021/ja512396m

Probing the single-wall carbon nanotube bundle: Raman scattering under high pressure
journal, April 1999


Nanoscale uranium-based cage clusters inspired by uranium mineralogy
journal, February 2011


Raman Spectroscopic and ESI-MS Characterization of Uranyl Peroxide Cage Clusters
journal, January 2014

  • McGrail, Brendan T.; Sigmon, Ginger E.; Jouffret, Laurent J.
  • Inorganic Chemistry, Vol. 53, Issue 3
  • DOI: 10.1021/ic402570b

Symmetry versus Minimal Pentagonal Adjacencies in Uranium-Based Polyoxometalate Fullerene Topologies
journal, March 2009

  • Sigmon, Ginger E.; Unruh, Daniel K.; Ling, Jie
  • Angewandte Chemie International Edition, Vol. 48, Issue 15
  • DOI: 10.1002/anie.200805870

Uranyl peroxide pyrophosphate cage clusters with oxalate and nitrate bridges
journal, January 2012

  • Ling, Jie; Ozga, Michael; Stoffer, Megan
  • Dalton Transactions, Vol. 41, Issue 24
  • DOI: 10.1039/c2dt30229b

Medium-range structural order in covalent amorphous solids
journal, December 1991


Pressure-Dependent Polymorphism and Band-Gap Tuning of Methylammonium Lead Iodide Perovskite
journal, April 2016

  • Jiang, Shaojie; Fang, Yanan; Li, Ruipeng
  • Angewandte Chemie International Edition, Vol. 55, Issue 22
  • DOI: 10.1002/anie.201601788

Red-to-Black Piezochromism in a Compressible Pb–I–SCN Layered Perovskite
journal, May 2016


Order from Disorder
journal, August 2012


Low-Symmetry Uranyl Pyrophosphate Cage Clusters
journal, January 2011

  • Ling, Jie; Qiu, Jie; Szymanowski, Jennifer E. S.
  • Chemistry - A European Journal, Vol. 17, Issue 9
  • DOI: 10.1002/chem.201003481

Uranyl peroxide enhanced nuclear fuel corrosion in seawater
journal, January 2012

  • Armstrong, C. R.; Nyman, M.; Shvareva, T.
  • Proceedings of the National Academy of Sciences, Vol. 109, Issue 6
  • DOI: 10.1073/pnas.1119758109

Experimental measurements of U60 nanocluster stability in aqueous solution
journal, May 2015

  • Flynn, Shannon L.; Szymanowski, Jennifer E. S.; Gao, Yunyi
  • Geochimica et Cosmochimica Acta, Vol. 156
  • DOI: 10.1016/j.gca.2015.02.021

Long-Range Ordered Carbon Clusters: A Crystalline Material with Amorphous Building Blocks
journal, August 2012


Water-soluble multi-cage super tetrahedral uranyl peroxide phosphate clusters
journal, January 2014

  • Qiu, Jie; Ling, Jie; Jouffret, Laurent
  • Chem. Sci., Vol. 5, Issue 1
  • DOI: 10.1039/C3SC52357H

Time-Resolved Self-Assembly of a Fullerene-Topology Core–Shell Cluster Containing 68 Uranyl Polyhedra
journal, January 2012

  • Qiu, Jie; Ling, Jie; Sui, Audrey
  • Journal of the American Chemical Society, Vol. 134, Issue 3
  • DOI: 10.1021/ja210163b

Uranium Pyrophosphate/Methylenediphosphonate Polyoxometalate Cage Clusters
journal, September 2010

  • Ling, Jie; Qiu, Jie; Sigmon, Ginger E.
  • Journal of the American Chemical Society, Vol. 132, Issue 38
  • DOI: 10.1021/ja1048219

Understanding the Structure and Formation of Uranyl Peroxide Nanoclusters by Quantum Chemical Calculations
journal, October 2010

  • Vlaisavljevich, Bess; Gagliardi, Laura; Burns, Peter C.
  • Journal of the American Chemical Society, Vol. 132, Issue 41
  • DOI: 10.1021/ja104964x

The influence of pressure on the photoluminescence properties of a terbium-adipate framework
journal, June 2013


Complex Nanoscale Cage Clusters Built from Uranyl Polyhedra and Phosphate Tetrahedra
journal, June 2011

  • Unruh, Daniel K.; Ling, Jie; Qiu, Jie
  • Inorganic Chemistry, Vol. 50, Issue 12
  • DOI: 10.1021/ic200065y

Uranyl Peroxide Oxalate Cage and Core–Shell Clusters Containing 50 and 120 Uranyl Ions
journal, January 2012

  • Ling, Jie; Qiu, Jie; Burns, Peter C.
  • Inorganic Chemistry, Vol. 51, Issue 4
  • DOI: 10.1021/ic202380g

Uranyl peroxide closed clusters containing topological squares
journal, January 2010

  • Unruh, Daniel K.; Burtner, Alicia; Pressprich, Laura
  • Dalton Transactions, Vol. 39, Issue 25
  • DOI: 10.1039/c0dt00074d

Fityk : a general-purpose peak fitting program
journal, September 2010


Metal–Oxygen Isopolyhedra Assembled into Fullerene Topologies
journal, March 2008

  • Forbes, Tori Z.; McAlpin, J. Gregory; Murphy, Rachel
  • Angewandte Chemie International Edition, Vol. 47, Issue 15
  • DOI: 10.1002/anie.200705563

Electrical and Mechanical Properties of C 70 Fullerene and Graphite under High Pressures Studied Using Designer Diamond Anvils
journal, December 2000

  • Patterson, Jeremy R.; Catledge, Shane A.; Vohra, Yogesh K.
  • Physical Review Letters, Vol. 85, Issue 25
  • DOI: 10.1103/PhysRevLett.85.5364

Uranyl Peroxide Cage Cluster Solubility in Water and the Role of the Electrical Double Layer
journal, January 2017


Time-Resolved Assembly of Chiral Uranyl Peroxo Cage Clusters Containing Belts of Polyhedra
journal, December 2012

  • Qiu, Jie; Nguyen, Kevin; Jouffret, Laurent
  • Inorganic Chemistry, Vol. 52, Issue 1
  • DOI: 10.1021/ic3020817